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Department of Chemistry, Karnatak University, Dharwad 580 003, India ... Experimental data on density, viscosity, and refractive index at (298.15, 303...
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J. Chem. Eng. Data 2001, 46, 891-896

891

Density, Viscosity, Refractive Index, and Speed of Sound for the Binary Mixtures of Ethyl Chloroacetate with n-Alkanes (C6 to C12) at (298.15, 303.15, and 308.15) K Jyoti N. Nayak, Mrityunjaya I. Aralaguppi,* and Tejraj M. Aminabhavi Department of Chemistry, Karnatak University, Dharwad 580 003, India

Experimental data on density, viscosity, and refractive index at (298.15, 303.15, and 308.15) K and the speed of sound at 298.15 K are presented for the binary mixtures of ethyl chloroacetate + hexane, heptane, octane, nonane, decane, or dodecane. From these data, excess molar volume, deviations in viscosity, molar refraction, and isentropic compressibility have been calculated. The computed quantities have been fitted to Redlich-Kister equation to derive the coefficients and estimate the standard error values.

Introduction The present paper is a part of our continuing study on the accumulation of binary mixture property data containing n-alkanes (Aminabhavi and Bindu, 1994; Aminabhavi et al., 1994, 1996, 1997; Aralaguppi et al., 1991, 1999). In this paper, ethyl chloroacetate (ECA) + n-alkane (hexane, heptane, octane, nonane, decane, and dodecane) mixtures have been studied. The alkanes have relevance in petrochemical industries, while ECA, due to its insecticidal activity, is used as a solvent in organic synthesis (Buckingham, 1982). Therefore, their binary mixture properties will be useful in industrial sectors. A survey of the literature indicates that no physical property data on these mixtures have been studied earlier. This prompted us to undertake a study on the measurement of density, F, viscosity, η, refractive index, nD, and speed of sound, u, at different temperatures. Using these data, excess molar volume, VE, and deviations in viscosity, ∆η, molar refraction, ∆R, and isentropic compressibility, ∆kS, have been calculated. These results were further fitted to the RedlichKister equation (Redlich and Kister, 1948) to derive the binary coefficients and estimate the standard errors. Experimental Section Materials. High-purity spectroscopic and HPLC grade samples of hexane and heptane were procured from Spectrochem Ltd. and s.d. fine Chemicals, Mumbai, India. Octane was of analytical reagent grade while nonane, decane, and dodecane were all laboratory reagent grade and were procured from s.d. fine Chemicals, Mumbai, India. Ethyl chloroacetate was purchased from BASCO, Mumbai, India. The mole percent purities of all the liquids as determined by GC (HP 6890) using a FID detector were >99 and are reported in Table 1. Density and refractive index data at 298.15 K for the pure liquids are compared with the literature values in Table 1. Binary mixtures were prepared by mass in specially designed glass-stoppered bottles (Aminabhavi et al., 1994). The mass measurements accurate to (0.01 mg were done on a digital electronic balance (Mettler, AE 240, Switzerland). A set of nine compositions was prepared for each * To whom correspondence [email protected].

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Table 1. Comparison of Experimental Densities (G) and Refractive Indices (nD) of Pure Liquids with Literature Values at 298.15 K liquid ethyl chloroacetate hexane heptane octane nonane decane dodecane

(mol % purity)

F/(kg‚m-3) expt lit.

nD expt

lit.

(>99.0) 1157.0a 1158.5a,b 1.4211a 1.4215a,b (>99.9) (>99.7) (>99.7) (>98.0) (>99.0) (>99.0)

654.7 679.3 698.5 714.1 726.0 744.9

654.8d 679.5d 698.5d 713.8c 726.4c 745.2c

1.3729 1.3859 1.3952 1.4039 1.4098 1.4199

1.3723c 1.3851c 1.3951c 1.4031c 1.4096c 1.4195c

a Measured and compared at 293.15 K. b CRC Handbook, 198283. c Riddick et al., 1986. d Marsh, 1994.

system, and their physical properties were measured at the respective compositions starting from 0.1 to 0.9 mole fraction in steps of 0.1. The possible error in mole fraction was estimated to be less than 10-4 in all the cases. Methods. Densities of liquids and liquid mixtures were measured to an accuracy of (0.0001 using a capillary pycnometer of about 10 cm3 volume as per the experimental details given earlier (Aralaguppi et al.,1991; Aminabhavi et al., 1994). Viscosities were measured using a Cannon Fenske viscometer (size 75, ASTM D 445 supplied by Industrial Research Glassware Ltd., Roselle, NJ). An electronic digital stopwatch with a readability of (0.01 s was used for the flow time measurements. The measured viscosity values are accurate to (0.001 mPa‚s. Calibrations of the pycnometer and viscometer are the same as described earlier (Aminabhavi and Bindu, 1994; Aminabhavi et al., 1994). Refractive indices for the sodium D-line were measured using a thermostatically controlled Abbe refractometer (Atago 3T, Japan). The minimum of three independent readings was taken for each composition, and their average value is used in all the calculations. The results of refractive indices are accurate to (0.0001 units. Speed of sound values were measured by using a variable-path single-crystal interferometer (Mittal Enterprises, New Delhi, Model M-84). A crystal-controlled highfrequency generator was used to excite the transducer at a frequency of 1 MHz. The frequency was measured within

10.1021/je010020w CCC: $20.00 © 2001 American Chemical Society Published on Web 06/01/2001

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Journal of Chemical and Engineering Data, Vol. 46, No. 4, 2001

Figure 1. Excess molar volume (VE) versus mole fraction of ethyl chloroacetate with (O) hexane, (4) heptane, (0) octane, (b) nonane, (2) decane, and (9) dodecane at 298.15 K.

Figure 2. Deviations in viscosity (∆η) versus mole fraction at 298.15 K for mixtures of ethyl chloroacetate with alkanes. Symbols are the same as given in Figure 1.

an accuracy of 1 in 104 using a digital frequency meter. The interferometer cell was filled with the test liquid, and water was circulated around the measuring cell from a thermostat maintained at 298.15 ( 0.01 K. To increase the accuracy of the measurement, several such maxima were counted by changing the distance between transducer and reflector. The total distance, d, moved by the reflector, which is fixed to the micrometer scale, corresponding to the two maxima in the ammeter, was measured and was used to calculate the wavelength, λ, by using d ) nλ/2. By knowing the frequency, ν, of the crystal (1 MHz), speed of sound, u, in m‚s-1 was calculated as u ) νλ. The speed of sound values thus calculated are accurate to (2 in 1000 m‚s-1. The isentropic compressibilities were calculated using kS ) 1/u2F (where u is in m‚s-1 and F in kg/m3). In all the above measurements, the temperature was controlled within (0.01 K using a constant temperature bath. A Julabo immersion cooler (FT 200, Julabo Labortechnik Gmbh, Germany) was used to cool the water bath. This unit was installed at the intake of a heating circulator to draw the heat away from the circulating bath liquid. The immersion probe was connected to the instrument with a flexible and insulated tube. To prevent the immersion probe from icing, it was completely immersed into the bath liquid. At least three independent readings of the physical properties were taken for each composition, and the averages of these results are given in Table 2. Results and Discussion The results of VE, ∆η, ∆R, and ∆kS of the mixtures have been calculated respectively using the results of F, η, nD,

Figure 3. Effect of temperature on ∆η for the ethyl chloroacetate + heptane mixture: (O) 298.15 K; (9) 303.15 K; (2) 308.15 K.

Figure 4. Deviations in molar refraction (∆R) versus volume fraction at 298.15 K for mixtures of ethyl chloroacetate with alkanes. Symbols are the same as given in Figure 1.

Figure 5. Deviations in isentropic compressibility (∆kS) versus volume fraction at 298.15 K for mixtures of ethyl chloroacetate with alkanes. Symbols are the same as given in Figure 1.

and u by using the relations (Aminabhavi and Bindu, 1994; Aminabhavi et al., 1996)

VE ) Vm - V1x1 - V2x2

(1)

∆Y ) Ym - Y1x1 - Y2x2

(2)

Here, Vm is molar volume of the mixture, V1 and V2 are the molar volumes of the pure components, xi represents the mole fraction of the ith component of the mixture, and ∆Y represents ∆η, ∆R, and ∆kS , respectively. Ym is the

Journal of Chemical and Engineering Data, Vol. 46, No. 4, 2001 893 Table 2. Experimental Density (G), Viscosity (η), Refractive Index (nD), and Speed of Sound (u) of Binary Mixtures at Different Temperatures x1

F/(kg‚m-3)

η/(mPa‚s)

nD

u/(m‚s-1)

x1

F/(kg‚m-3)

0.0000 0.0977 0.2029 0.3028 0.4001 0.4982

654.7 693.5 737.5 781.2 825.6 872.4

0.318 0.342 0.375 0.416 0.465 0.524

Ethyl Chloroacetate (1) + Hexane (2) 298.15 K 1.3729 1081 0.6039 925.4 1.3762 1089 0.7027 977.0 1.3804 1102 0.8032 1031.9 1.3844 1118 0.9022 1088.1 1.3886 1137 1.0000 1146.1 1.3933 1159

0.0000 0.0977 0.2029 0.3028 0.4001 0.4982

649.4 688.5 732.2 775.8 820.0 866.7

0.303 0.326 0.357 0.396 0.441 0.495

1.3695 1.3733 1.3777 1.3819 1.3862 1.3910

0.0000 0.0977 0.2029 0.3028 0.4001 0.4982

645.0 683.5 726.9 770.3 814.4 860.9

0.288 0.309 0.339 0.377 0.417 0.466

1.3668 1.3706 1.3749 1.3794 1.3839 1.3887

η/(mPa‚s)

nD

u/(m‚s-1)

0.602 0.683 0.787 0.923 1.097

1.3988 1.4040 1.4095 1.4147 1.4200

1182 1200 1218 1234 1249

303.15 K 0.6039 0.7027 0.8032 0.9022 1.0000

919.4 970.8 1025.4 1081.6 1139.3

0.566 0.641 0.739 0.861 1.007

1.3964 1.4016 1.4070 1.4123 1.4173

0.6039 0.7027 0.8032 0.9022 1.0000

913.4 964.6 1019.1 1075.1 1132.8

0.530 0.600 0.690 0.800 0.933

1.3940 1.3992 1.4046 1.4098 1.4147

0.651 0.726 0.817 0.930 1.097

1.4022 1.4062 1.4100 1.4148 1.4200

308.15 K

0.0000 0.1037 0.2030 0.3009 0.4005 0.4992

679.3 713.9 749.4 787.1 828.2 871.6

0.404 0.419 0.450 0.484 0.530 0.585

Ethyl Chloroacetate (1) + Heptane (2) 298.15 K 1.3859 1123 0.6048 921.8 1.3873 1123 0.7050 973.4 1.3897 1124 0.8022 1026.3 1.3920 1125 0.8954 1080.4 1.3955 1128 1.0000 1146.1 1.3982 1139

0.0000 0.1037 0.2030 0.3009 0.4005 0.4992

674.8 709.3 744.2 781.7 823.1 866.6

0.381 0.398 0.424 0.457 0.498 0.545

1.3827 1.3845 1.3867 1.3893 1.3923 1.3955

0.0000 0.1037 0.2030 0.3009 0.4005 0.4992

670.5 704.7 739.5 776.9 817.6 860.9

0.363 0.378 0.402 0.432 0.469 0.522

1.3801 1.3816 1.3841 1.3863 1.3898 1.3928

1160 1188 1211 1233 1249

303.15 K 0.6048 0.7050 0.8022 0.8954 1.0000

915.5 967.0 1020.0 1073.6 1139.3

0.608 0.676 0.761 0.859 1.007

1.3995 1.4033 1.4078 1.4122 1.4173

0.6048 0.7050 0.8022 0.8954 1.0000

910.1 961.1 1014.0 1067.6 1132.8

0.569 0.634 0.710 0.800 0.933

1.3966 1.4012 1.4052 1.4096 1.4147

0.718 0.782 0.855 0.953 1.097

1.4057 1.4086 1.4119 1.4157 1.4200

308.15 K

0.0000 0.1027 0.2003 0.3048 0.4033 0.5064

698.5 727.7 758.1 794.1 831.1 873.3

0.503 0.524 0.553 0.586 0.618 0.666

Ethyl Chloroacetate (1) + Octane (2) 298.15 K 1.3952 1167 0.6021 916.4 1.3966 1176 0.7042 966.3 1.3974 1182 0.8031 1020.1 1.3991 1189 0.9017 1079.3 1.4010 1194 1.0000 1146.1 1.4030 1202

0.0000 0.1027 0.2003 0.3048 0.4033 0.5064

694.2 723.1 734.3 789.4 826.0 868.5

0.472 0.493 0.518 0.551 0.577 0.621

1.3932 1.3936 1.3948 1.3961 1.3982 1.4006

0.0000 0.1027 0.2003 0.3048 0.4033 0.5064

690.0 718.8 748.9 784.4 820.8 862.7

0.445 0.465 0.487 0.519 0.541 0.584

1.3906 1.3911 1.3922 1.3938 1.3955 1.3981

0.656 0.660 0.665 0.686 0.716 0.755

Ethyl Chloroacetate (1) + Nonane (2) 298.15 K 1.4039 1211 0.6012 912.4 1.4040 1212 0.7037 961.6 1.4042 1215 0.8037 1016.3 1.4050 1218 0.9012 1075.8 1.4060 1225 1.0000 1146.1 1.4073 1230

1209 1217 1230 1241 1249

303.15 K 0.6021 0.7042 0.8031 0.9017 1.0000

911.0 961.2 1013.7 1072.9 1139.3

0.669 0.723 0.796 0.884 1.007

1.4032 1.4063 1.4090 1.4130 1.4173

0.6021 0.7042 0.8031 0.9017 1.0000

905.4 955.2 1008.5 1066.9 1132.8

0.624 0.676 0.741 0.820 0.934

1.4003 1.4036 1.4062 1.4113 1.4147

0.799 0.849 0.907 0.982 1.097

1.4088 1.4109 1.4133 1.4164 1.4200

308.15 K

0.0000 0.1004 0.2033 0.3013 0.4018 0.5019

714.1 739.2 768.1 798.3 832.3 870.3

1235 1241 1245 1248 1249

894

Journal of Chemical and Engineering Data, Vol. 46, No. 4, 2001

Table 2. (Continued) x1

F/(kg‚m-3)

η/(mPa‚s)

nD

u/(m‚s-1)

x1

F/(kg‚m-3)

0.0000 0.1004 0.2033 0.3013 0.4018 0.5019

710.3 734.7 763.3 793.0 827.3 865.3

0.613 0.620 0.623 0.644 0.670 0.705

Ethyl Chloroacetate (1) + Nonane (2) 303.15 K 1.4013 0.6012 907.3 1.4013 0.7037 956.8 1.4017 0.8037 1010.0 1.4024 0.9012 1069.3 1.4033 1.0000 1139.3 1.4048

0.0000 0.1004 0.2033 0.3013 0.4018 0.5019

706.2 730.2 758.6 788.2 822.3 860.2

0.575 0.580 0.583 0.602 0.624 0.654

1.3984 1.3987 1.3992 1.4000 1.4007 1.4023

η/(mPa‚s)

nD

0.743 0.792 0.842 0.912 1.007

1.4060 1.4083 1.4106 1.4137 1.4173

0.688 0.735 0.778 0.843 0.934

1.4032 1.4056 1.4078 1.4112 1.4147

0.897 0.930 0.969 1.024 1.097

1.4118 1.4130 1.4148 1.4170 1.4200

u/(m‚s-1)

308.15 K 0.6012 0.7037 0.8037 0.9012 1.0000

902.1 950.8 1003.8 1062.9 1132.8

0.0000 0.0992 0.2037 0.3031 0.4005 0.5016

726.0 748.0 774.4 802.4 833.2 869.5

0.820 0.821 0.825 0.828 0.843 0.869

Ethyl Chloroacetate (1) + Decane (2) 298.15 K 1.4098 1228 0.6027 910.5 1.4099 1229 0.7039 957.4 1.4100 1231 0.8019 1009.9 1.4103 1233 0.9008 1071.7 1.4104 1236 1.0000 1146.1 1.4112 1238

0.0000 0.0992 0.2037 0.3031 0.4005 0.5016

729.1 743.8 770.0 796.8 828.6 864.4

0.755 0.761 0.766 0.767 0.780 0.801

1.4071 1.4072 1.4074 1.4075 1.4077 1.4086

0.0000 0.0992 0.2037 0.3031 0.4005 0.5016

717.0 739.9 765.4 792.8 823.5 859.1

0.711 0.707 0.713 0.719 0.725 0.742

1.4045 1.4047 1.4048 1.4048 1.4054 1.4060

1241 1244 1246 1248 1249

303.15 K 0.6027 0.7039 0.8019 0.9008 1.0000

904.3 951.6 1003.9 1065.9 1139.3

0.827 0.854 0.885 0.946 1.007

1.4092 1.4106 1.4121 1.4142 1.4173

0.6027 0.7039 0.8019 0.9008 1.0000

899.5 946.0 998.3 1059.6 1132.8

0.765 0.791 0.829 0.872 0.934

1.4068 1.4078 1.4096 1.4114 1.4147

1.116 1.105 1.101 1.099 1.097

1.4170 1.4170 1.4172 1.4182 1.4200

308.15 K

0.0000 0.0961 0.2041 0.3012 0.4005 0.5029

744.9 762.4 784.6 807.8 834.7 867.2

1.330 1.250 1.197 1.159 1.140 1.127

Ethyl Chloroacetate (1) + Dodecane (2) 298.15 K 1.4199 1287 0.6026 904.0 1.4191 1279 0.7029 948.0 1.4182 1274 0.8040 1002.3 1.4178 1272 0.9017 1065.5 1.4175 1271 1.0000 1146.1 1.4170 1267

0.0000 0.0961 0.2041 0.3012 0.4005 0.5029

740.9 758.4 780.8 802.9 830.6 862.6

1.209 1.149 1.094 1.062 1.041 1.027

1.4179 1.4169 1.4162 1.4156 1.4150 1.4147

0.0000 0.0961 0.2041 0.3012 0.4005 0.5029

737.6 754.6 776.3 798.8 825.7 857.7

1.111 1.054 1.019 0.979 0.960 0.946

1.4152 1.4148 1.4136 1.4131 1.4128 1.4121

1264 1258 1252 1250 1249

303.15 K 0.6026 0.7029 0.8040 0.9017 1.0000

899.5 942.3 996.2 1058.8 1139.3

1.029 1.015 0.994 0.985 1.007

1.4145 1.4145 1.4147 1.4156 1.4173

0.6026 0.7029 0.8040 0.9017 1.0000

893.9 937.4 989.9 1053.3 1132.8

0.940 0.930 0.927 0.929 0.934

1.4120 1.4120 1.4120 1.4126 1.4147

308.15 K

respective mixture property, viz., molar refractivity, R (calculated from the Lorenz-Lorentz relation), viscosity, η, speed of sound, u, and isentropic compressibility, kS, for the binary mixtures; Yi refers to pure component properties. While calculating the ∆R and ∆kS values, the volume fraction, φi, was used (Aminabhavi and Bindu, 1994; Aminabhavi et al., 1996, 1997). However, for the calculation of VE and ∆η, mole fraction was used. The excess molar volume data displayed at 298.15 K in Figure 1 are positive in all the cases, indicating volume expansion upon mixing the alkanes with ethyl chloroacetate. The points on the curves represent the VE values calculated from eq 1, while the smooth curves are drawn from the best fitted values of VE calculated from eq 3. A

large positive VE (1.3 cm3/mol) for the ethyl chloroacetate + dodecane mixture and a small VE value of 0.23 cm3/mol for the ethyl chloroacetate + hexane mixture signify that, with increasing size of alkane, the volume expansion becomes considerably larger. The equimolar values of VE for mixtures of ethyl chloroacetate + nonane or + decane are almost identical, signifying not much difference in the interactions between these mixtures. The VE results at other temperatures follow the same trends, but these are not displayed in order to avoid the redundancy of graphical presentations. However, there is no effect of temperature on excess volume. The ∆η versus x1 plots at 298.15 K displayed in Figure 2 show negative deviations in all the mixtures; also, these

Journal of Chemical and Engineering Data, Vol. 46, No. 4, 2001 895 Table 3. Estimated Parameters of Eq 3 for Various Functions of the Binary Mixtures at Different Temperatures function

temp/K

A0

A1

A2

σ

Ethyl Chloroacetate (1) + Hexane (2) 106VE/(m3‚mol-1) 298.15 0.893 1.071 0.110 303.15 0.650 0.786 -0.260 308.15 0.828 1.021 0.312 ∆η/(mPa‚s) 298.15 -0.727 0.288 -0.209 303.15 -0.634 0.218 -0.114 308.15 -0.573 0.204 -0.100 298.15 -0.471 0.162 0.108 106∆R/(m3‚mol-1) 303.15 -0.352 0.113 0.190 308.15 -0.224 0.085 0.151 ∆kS/(T Pa-1) 298.15 -479.9 4.03 114.9

0.013 0.015 0.005 0.002 0.002 0.001 0.008 0.005 0.003 1.138

Ethyl Chloroacetate (1) + Heptane (2) 106VE/(m3‚mol-1) 298.15 1.926 1.661 0.148 303.15 1.946 1.676 0.675 308.15 2.138 1.788 0.343 ∆η/(mPa‚s) 298.15 -0.665 0.246 -0.229 303.15 -0.590 0.210 -0.168 308.15 -0.526 0.184 -0.181 6 3 -1 10 ∆R/(m ‚mol ) 298.15 -2.450 0.255 -0.216 303.15 -2.400 0.299 0.170 308.15 -2.371 0.367 -0.058 ∆kS/(T Pa-1) 298.15 -150.4 -162.6 -116.0

0.035 0.051 0.033 0.002 0.002 0.004 0.018 0.014 0.024 6.381

Ethyl Chloroacetate (1) + Octane (2) 106VE/(m3‚mol-1) 298.15 2.984 1.008 1.562 303.15 2.550 9.364 17.71 308.15 3.118 1.307 1.038 ∆η/(mPa‚s) 298.15 -0.542 0.280 -0.198 303.15 -0.482 0.244 -0.126 308.15 -0.435 0.224 -0.128 106∆R/(m3‚mol-1) 298.15 -4.966 0.912 0.341 303.15 -5.392 -0.137 4.095 308.15 -5.074 1.140 0.062 -1 ∆kS/(T Pa ) 298.15 -227.0 46.04 -52.12

0.020 1.483 0.018 0.006 0.005 0.006 0.010 0.313 0.048 0.791

Ethyl Chloroacetate (1) + Nonane (2) 106VE/(m3‚mol-1) 298.15 3.792 0.592 -0.025 303.15 3.881 1.461 1.155 308.15 4.021 1.562 2.124 ∆η/(mPa‚s) 298.15 -0.489 0.129 -0.227 303.15 -0.426 0.098 -0.137 308.15 -0.401 0.111 -0.144 106∆R/(m3‚mol-1) 298.15 -8.446 2.119 -0.633 303.15 -8.465 1.961 -0.102 308.15 -8.434 1.804 0.382 ∆kS/(T Pa-1) 298.15 -200.2 5.110 35.55

0.050 0.073 0.059 0.006 0.003 0.003 0.020 0.017 0.016 1.495

Ethyl Chloroacetate (1) + Decane (2) 106VE/(m3‚mol-1) 298.15 3.805 0.3130 1.416 303.15 7.687 7.003 9.738 308.15 3.883 -0.362 -0.691 ∆η/(mPa‚s) 298.15 -0.364 0.096 -0.063 303.15 -0.327 0.120 -0.017 308.15 -0.320 0.095 -0.035 6 3 -1 10 ∆R/(m ‚mol ) 298.15 -12.53 3.549 -0.442 303.15 -11.44 1.697 2.299 308.15 -12.49 3.520 -1.202 ∆kS/(TPa1-) 298.15 -159.1 21.60 9.430

0.032 0.218 0.102 0.005 0.007 0.003 0.001 0.111 0.025 0.200

Ethyl Chloroacetate (1) + Dodecane (2) 106VE/(m3‚mol-1) 298.15 5.165 -0.386 0.448 303.15 4.983 -0.692 1.112 308.15 5.634 -0.244 1.181 ∆η/(mPa‚s) 298.15 -0.350 -0.234 -0.151 303.15 -0.300 -0.132 -0.246 308.15 -0.303 -0.110 -0.051 106∆R/(m3‚mol-1) 298.15 -22.04 8.203 -3.501 303.15 -22.13 8.429 -3.371 308.15 -21.95 7.944 -3.131 -1 ∆kS/(T Pa ) 298.15 -55.77 4.59 72.75

0.041 0.067 0.036 0.003 0.010 0.004 0.037 0.037 0.028 2.86

data show a systematic increase from hexane to dodecane. For the ethyl chloroacetate + dodecane mixture, the ∆η values show a slight decreasing trend in the lower mole fraction range. At higher temperatures, ∆η versus x1 plots exhibit the same dependencies, but these values increase

systematically with increasing temperature for all the mixtures. A typical graph displaying the effect of temperature on the ∆η versus x1 plot for the ethyl chloroacetate + heptane mixture is shown in Figure 3. The results of ∆R and ∆kS versus φ1 (volume fraction of ethyl chloroacetate) at 298.15 K are presented respectively in Figures 4 and 5. Both these parameters exhibit negative deviations in all the mixtures, further supporting weak (dispersion-type) intermolecular interactions between the mixing components. The values of ∆R decrease with increasing size of alkanes, while a reverse trend is seen for the dependence of ∆kS on volume fraction. The effect of temperature on ∆R is not considerable in all the binary mixtures, except ethyl chloroacetate + hexane mixtures, for which ∆R increases systematically with increasing temperature. The mixing quantities, viz., VE, ∆η, ∆R, and ∆kS, have been fitted to the Redlich-Kister (Redlich and Kister, 1948) equation by the method of least-squares using the Marquardt algorithm (Marquardt, 1963) to derive the binary coefficient, Ai, and the standard deviation, σ: k

VE(∆Y) ) x1x2

∑ A (x j

2

- x1)j-1

(3)

j)1

In each case, the optimum number of coefficients, Aj, was ascertained from an examination of the variation of the standard deviation, σ, with n,

σ)

(

∑(Y

E cal

)

- YEobs)2

(n - m)

1/2

(4)

where n represents the number of measurements and m the number of coefficients. The estimated values of Aj and σ for VE, ∆η, ∆R, and ∆kS are summarized in Table 3. In all the cases, the best fit was obtained by using only three fitting coefficients in all the cases. Acknowledgment This research was funded by the Department of Science and Technology, New Delhi, India (SP/S1/H-09/200). Literature Cited Aminabhavi, T. M.; Bindu, G. Densities, Shear Viscosities, Refractive Indices, and Speeds of Sound of Bis(2-methoxyethyl) Ether with Nonane, Decane, Dodecane, Tetradecane, and Hexadecane at 298.15, 308.15, and 318.15 K. J. Chem. Eng. Data 1994, 39, 529534. Aminabhavi, T. M.; Aralaguppi, M. I.; Bindu, G.; Khinnavar, R. S. Densities, Shear Viscosities, Refractive Indices, and Speeds of Sound of Bis(2-methoxyethyl) Ether with Hexane, Heptane, Octane, and 2,2,4-Trimethylpentane in the Temperature Interval 298.15 to 318.15 K. J. Chem. Eng. Data 1994, 39, 522-528. Aminabhavi, T. M.; Phayde, H. T. S.; Khinnavar, R. S.; Bindu, G. Densities, Refractive Indices, Speeds of Sound, and Shear Viscosities of Diethylene Glycol Dimethyl Ether with Ethyl Acetate, Methyl Benzoate, Ethyl Benzoate, and Diethyl Succinate in the Temperature Range from 298.15 to 318.15 K. J. Chem. Eng. Data 1994, 39, 251-260. Aminabhavi, T. M.; Patil, V. B.; Aralaguppi, M. I.; Phayde, H. T. S. Density, Viscosity, and Refractive Index of the Binary Mixtures of Cyclohexane with Hexane, Heptane, Octane, Nonane, and Decane at (298.15, 303.15 and 308.15) K. J. Chem. Eng. Data 1996, 41, 521525. Aminabhavi, T. M.; Patil, V. B.; Aralaguppi, M. I.; Ortego, J. D.; Hansen, K. C. Density, Refractive Index, Viscosity, and Speed of Sound in Binary Mixtures of Ethenylbenzene with Hexane, Heptane, Octane, Nonane Decane, and Dodecane. J. Chem. Eng. Data 1997, 42, 641-646. Aralaguppi, M. I.; Aminabhvi, T. M.; Balundgi, R. H.; Joshi, S. S. Thermodynamic Interactions in Mixtures of Bromoform with Hydrocarbons. J. Phys. Chem. 1991, 95, 5299-5308.

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Aralaguppi, M. I.; Jadar, C. V.; Aminabhavi, T. M. Density, Refractive Index, Viscosity, and Speed of Sound in Binary Mixtures of 2-Ethoxyethanol with Dioxane, Acetonitrile, and Tetrahydrofuran, at (298.15, 303.15 and 308.15) K. J. Chem. Eng. Data 1996, 41, 1307-1310. Aralaguppi, M. I.; Jadar, C. V.; Aminabhavi, T. M. Density, Viscosity, Refractive Index, and Speed of Sound in Binary Mixtures of 2-Chloroethanol with Methyl Acetate, Ethyl Acetate, n-Propyl Acetate, and n-Butyl Acetate. J. Chem. Eng. Data 1999, 44, 441445. Aralaguppi, M. I.; Jadar, C. V.; Aminabhavi, T. M. Density, Viscosity, Refractive Index, and Speed of Sound in Binary Mixtures of Cyclohexanone with Hexane, Heptane, Octane, Nonane, Decane, Dodecane, and 2,2,4-Trimethylpentane. J. Chem. Eng. Data 1999, 44, 435-440. Buckingham, J., Ed. Dictionary of Organic Compounds, 3rd ed.; Chapman & Hall: London, 1982; Vol. 3.

CRC Handbook of Chemistry and Physics, 63rd ed.; Weast, R. C., Astle, M. J., Eds.; CRC Press: Boca Raton, FL, 1982-1983. Marquardt, D. W. An Algorithm for Least Squares Estimation of Nonlinear Parameters. J. Soc. Ind. Appl. Math. 1963, 11, 431-441. Marsh, K. N. Data Bases for Chemistry and Engineering, TRC Thermodynamic Tables; Texas A & M University System: 1994. Redlich, O.; Kister, A. T. Algebraic Representation of Thermodynamic Properties and the Classification of Solutions. Ind. Eng. Chem. 1948, 40, 345-348. Riddick, J. A.; Bunger, W. B.; Sakano, T. K. Techniques of Chemistry, Organic Solvents. Physical Properties and Methods of Purifications; John Wiley & Sons: New York, 1986; Vol. II. Received for review January 17, 2001. Accepted April 5, 2001.

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